Di­propyl 3,6‐di­phenyl‐1,2‐di­hydro‐1,2,4,5‐tetrazine‐1,2‐di­carboxyl­ate

The title compound, C₂₂H₂₄N₄O₄, was prepared from propyl chloro­formate and 3,6‐di­phenyl‐1,2‐di­hydro‐s‐tetrazine. This reaction yields the title compound rather than di­propyl 3,6‐di­phenyl‐1,4‐di­hydro‐s‐tetrazine‐1,4‐di­carboxyl­ate. The 2,3‐di­aza­buta­diene group in the central six‐membered ring is not planar; the C=N double‐bond length is 1.285 (2) Å, and the average N—N single‐bond length is 1.401 (3) Å, indicating a lack of conjugation. The ring has a twist conformation, in which adjacent N atoms lie 0.3268 (17) Å from the plane of the ring. The mol­ecule has twofold crystallographic symmetry.     

9,10‐Di­methoxy‐4‐methyl‐1,2‐di­hydro‐1‐aza­anthracen‐2‐one (kalasin­amide), a new aza­anthracene alkaloid

A new aza­anthracene alkaloid, namely 9,10‐di­methoxy‐4‐methyl‐1,2‐di­hydro‐1‐aza­anthracen‐2‐one (kalasin­amide), C₁₆H₁₅NO₃, has been isolated from the stems of Polyal­thia suberosa collected in the northeastern part of Thailand. Each of the aromatic rings in the mol­ecule is planar within 0.021 (2) Å. Molecules are linked to form centrosymmetric dimers by N—H?O hydrogen bonds [N?O 2.941 (4) Å].     

Diethyl 9,10‐di­hydro‐9,10‐ethano­anthracene‐11,12‐trans‐di­carboxyl­ate

The title compound, C₂₂H₂₂O₄, is the product of the Diels–Alder reaction of anthracene with fumaric acid diethyl ester. The molecular C₂ symmetry is nearly fulfilled in the crystal. Only the terminal torsion angles about the O—CH₂ groups show significant differences.     

7,8‐Di­phenyl‐9‐di­methyl­sulfido‐10,11‐μ‐hydro‐7,8‐dicarba‐nido‐undecaborane(9)

In the title compound, C₁₆H₂₅B₉S, there are two crystallographically independent mol­ecules, and the conformations of the phenyl and SMe₂ substituents indicate some intramolecular steric crowding. The bridging H atom is asymmetrically disposed. The title compound is a precursor to a crowded vertex‐labelled nido carborane ligand important in establishing the mechanism of isomerization of icosahedral heteroboranes.     

2,3,6,7‐Tetra­hydroxy‐9,10‐di­methyl‐9,10‐di­hydro‐9,10‐ethano­anthracene bis(1,4‐dioxane) solvate

2,3,6,7‐Tetra­hydroxy‐9,10‐di­methyl‐9,10‐di­hydro‐9,10‐ethano­anthracene crystallizes with 1,4‐dioxane to give a bis‐solvate, C₁₈H₁₈O₄·2C₄H₈O₂. The bis­(catechol) mol­ecule is located on a twofold axis and the two aromatic rings form a dihedral angle of 130.61 (4)°. Hydro­gen bonds are formed between the hydroxyl groups and either a neighbouring bis­(catechol) mol­ecule or the ether‐O atom of a dioxane mol­ecule.     

5,6‐Di­phenyl­[1,3]­di­thiolo­[4,5‐b]di­thiine‐2‐thione

In the title compound, C₁₇H₁₀S₅, the dithiine ring adopts a boat conformation while the di­thiole ring has an envelope conformation. The phenyl groups are planar and make dihedral angles of 40.7 (2) and 59.8 (2)° with the best plane of the thiine ring. The shortest intermolecular S?S contact is 3.305 (2) Å.     

A second polymorphic form of N,N′‐di­phenyl‐1,4‐phenyl­ene­di­amine

A new triclinic polymorphic form of N,N′‐di­phenyl‐1,4‐phenyl­ene­di­amine (C₆H₅NHC₆H₄NHC₆H₅) has been obtained through appropriate recrystallization of the orthorhombic form. It crystallized in the centrosymmetric space group P, with two half mol­ecules as the asymmetric unit.     

1‐Chloro‐3,6‐di­methoxy‐2,5‐di­methyl­benzene and 1‐chloro‐3,6‐di­methoxy‐2,4‐di­methyl­benzene

The title compounds, 1‐chloro‐3,6‐di­methoxy‐2,5‐di­methyl­benzene, (IIIa), and 1‐­chloro‐3,6‐di­methoxy‐2,4‐di­methyl­benzene, (IIIb), both C₁₀H₁₃ClO₂, were obtained from 2,5‐ and 2,6‐di­methyl‐1,4‐benzo­quinone, respectively, and are intermediates in the synthesis of ammonium quinone derivatives. The isomers have different substituents around the methoxy groups and crystallize in different space groups. In both mol­ecules, the methoxy groups each have different orientations with respect to the benzene ring. In both cases, one methoxy group lies in the plane of the ring and can participate in conjugation with the aromatic system, while the second is almost perpendicular to the plane of the aromatic ring. The C—O—C bond angles around these substituents are also different: 117.5 (4) and 118.2 (3)° in (IIIa) and (IIIb), respectively, when the methoxy groups lie in the plane of the ring, and 114.7 (3) and 113.6 (3)° in (IIIa) and (IIIb), respectively, when they are out of the plane of the ring.     

Three methoxy‐substituted diethyl 4‐­phenyl‐2,6‐di­methyl‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate compounds

Diethyl 4‐(2,5‐di­methoxy­phenyl)‐2,6‐di­methyl‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate, C₂₁H₂₇NO₆, (I), diethyl 4‐(3,4‐di­methoxy­phenyl)‐2,6‐di­methyl‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate, C₂₁H₂₇NO₆, (II), and diethyl 2,6‐di­methyl‐4‐(3,4,5‐tri­methoxy­phenyl)‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate, C₂₂H₂₉NO₇, (III), crystallize with hydrogen‐bonding networks involving the H atom bonded to the N atom of the 1,4‐di­hydro­pyridine ring and carbonyl O atoms in (I) and (II). Unusually, (III) shows O atoms of methoxy groups serving as hydrogen‐bond acceptors.     

4,8‐Di­methoxy‐1‐naphthalene­methanol

The title compound, C₁₃H₁₄O₃, crystallized in the centrosymmetric space group C2/c with one mol­ecule as the asymmetric unit. Each hydroxyl O atom is involved in hydrogen bonds with two other hydroxyl O atoms. The resulting chains of interactions propagate along [001]. In these interactions, the hydroxyl H atoms are disordered and the O?O distances are 2.648 (2) and 2.698 (2) Å. Two leading intermolecular C—H?O interactions have H?O distances of 2.80 and 2.84 Å and C—H?O angles of 136 and 144°; these interactions form chain and ring patterns. Taken together with the hydrogen bonds, they result in a three‐dimensional network.     

2,4‐Di­nitro­phenyl­hydrazones of 2,4‐di­hydroxy­benz­aldehyde, 2,4‐di­hydroxy­aceto­phenone and 2,4‐di­hydroxy­benzo­phenone

In 2,4‐di­hydroxy­benz­aldehyde 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­form­amide solvate {or 4‐[(2,4‐di­nitro­phenyl)­hydrazono­methyl]­benzene‐1,3‐diol N,N‐di­methyl­form­amide solvate}, C₁₃H₁₀N₄O₆·C₃H₇NO, (X), 2,4‐di­hydroxy­aceto­phenone 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­form­am­ide solvate (or 4‐{1‐[(2,4‐di­nitro­phenyl)hydrazono]ethyl}benzene‐1,3‐diol N,N‐di­methyl­form­amide solvate), C₁₄H₁₂N₄O₆·C₃H₇NO, (XI), and 2,4‐di­hydroxy­benzo­phenone 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­acet­amide solvate (or 4‐­{[(2,4‐di­nitro­phenyl)hydrazono]phenyl­methyl}benzene‐1,3‐diol N,N‐di­methyl­acet­amide solvate), C₁₉H₁₄N₄O₆·C₄H₉NO, (XII), the molecules all lack a center of symmetry, crystallize in centrosymmetric space groups and have been observed to exhibit non‐linear optical activity. In each case, the hydrazone skeleton is fairly planar, facilitated by the presence of two intramolecular hydrogen bonds and some partial N—N double‐bond character. Each molecule is hydrogen bonded to one solvent mol­ecule.     

A comparison of 2,7‐di­hydro‐2,2,7,7‐tetra­methyl‐3,6‐di­phenyl‐1,4,5‐thiadiazepine and the corresponding 1,1‐­dioxide

The structures of the highly substituted title heterocycles, C₂₀H₂₂N₂S and C₂₀H₂₂N₂O₂S, have been determined at 123 (1) K. Both mol­ecules possess exact C₂ symmetry and the seven‐membered rings have very similar twist‐boat conformations. The magnitudes of the C—S—C bond angles, 107.13 (6) and 108.27 (7)°, respectively, are influenced significantly by the four substituent methyl groups on the seven‐membered rings.     

6‐(1‐Hydro­xy‐2,2‐di­phenyl­ethyl)‐4,4‐di­phenyl‐2‐cyclo­hexen‐1‐one

The crystal structure of the title compound, C₃₂H₂₈O₂, (I), confirms the erythro stereochemistry of the aldol adduct. In the crystal, (I) forms centrosymmetric O—H?O=C hydrogen‐bonded dimers which in turn are connected by C—H?O and C—H?π interactions.     

4‐(Di­phenyl­phosphinoyl)‐3‐methyl‐N‐phenyl‐1,2‐isoxazole‐5‐carbox­amide

The title compound, C₂₃H₁₉N₂O₃P, was prepared by the reaction of ethynyldi­phenyl­phosphine oxide with phenyl isocyanate, triethyl­amine and nitoethane in benzene. The molecular structure is stabilized by an intramolecular N—H?O hydrogen bond.     

2,6‐Di­phenyl­pyridine‐4‐carboxyl­ic acid

The distinctive feature of the crystal structure of 2,6‐di­phenyl­pyridine‐4‐carboxyl­ic acid, C₁₈H₁₃NO₂, is the formation of intermolecular O—H?O hydrogen bonds that lead to the formation of centrosymmetric cyclic dimers with R(8) topology. Molecules related by translation along the b axis exhibit strong π–π stacking of aromatic rings, with an average interplanar distance of 3.3 Å.     

2‐Chloro‐4,6‐di­methoxy‐1,3,5‐triazine

The mol­ecules of 2‐chloro‐4,6‐di­methoxy‐1,3,5‐triazine, C₅H₆ClN₃O₂, lie on a crystallographic mirror plane. There is a close contact of 3.180 (3) Å between one of the methyl C atoms and the N atom of a neighboring mol­ecule. Differential scanning calorimetry measurements show that methyl rearrangement does not take place in the solid state, despite the close proximity of the methyl group to the N atom.     

4‐[N,N‐Bis(2‐hydroxy­imino‐2‐phenyl­ethyl)­amino]‐1,5‐di­methyl‐2‐phenyl‐2,3‐di­hydro‐1H‐pyrazol‐3‐one monohydrate

The title compound, C₂₇H₂₇N₅O₃·H₂O, is built up from pyrazolinone, phenyl and aceto­phenone oxime moieties. The 2‐­phenyl substituent is nearly perpendicular to the pyrazo­linone ring, with a dihedral angle of 87.66 (1)°. The aceto­phenone oxime moieties are twisted out of the pyrazolinone‐ring plane by 47.04 (1)°. The mol­ecules in the crystal pack in an antiparallel fashion and are held together by hydrogen‐bonded water mol­ecules and intermolecular O—H⋯O and O—H⋯N hydrogen bonds.     

Di­chloro­bis(3,5‐di­methyl­pyrazole‐N2)methyl­phenyl­tin(IV)

The title compound, [SnCl₂(CH₃)(C₆H₅)(C₅H₈N₂)₂], was obtained by reaction of di­chloro­methyl­phenyl­tin(IV) and 3,5‐di­methyl­pyrazole (dmpz) in chloro­form, and was recrystallized from acetone. The structure consists of octahedral all‐trans [SnMePhCl₂(dmpz)₂] mol­ecules, with the Sn atom coordinated to two C [Sn—C 2.127 (5) and 2.135 (4) Å], two Cl [Sn—Cl 2.5753 (8) Å] and two N atoms [Sn—N 2.357 (3) Å]. The dmpz ligands, bound to the metal through their unprotonated N atoms, form weak intra‐ and intermolecular hydrogen bonds with the Cl ligands via their NH groups, giving rise to a polymeric chain along the c axis.     

Derivatives of 4‐(2‐hydro­xy­lphenyl)‐2‐phenyl‐2,3‐di­hydro‐1,5‐benzothiazepine

In the structures of 2‐(4‐chloro­phenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐di­hydro‐1,5‐benzo­thia­zepine, C₂₁H₁₆ClNOS, 4‐(2‐hy­droxy­phenyl)‐2‐(4‐tolyl)‐2,3‐di­hydro‐1,5‐ben­zo­thia­zepine, C₂₂H₁₉NOS, and 4‐(2‐hydroxyphenyl)‐2‐(3‐methoxy­phenyl)‐2,3‐di­hydro‐1,5‐benzo­thia­zepine, C₂₂H₁₉NO₂S, the central seven‐membered heterocyclic rings adopt twist‐boat conformations in which the N atoms are involved in strong intramolecular hydrogen bonds with the hydroxyl H atoms, resulting in six‐membered rings.     

trans‐Di­chloro(1,12‐di­phenyl‐5,8‐dioxa‐2,11‐di­thia­do­decane‐S,S′)pal­ladium(II)

In the title compound, [PdCl₂(C₂₀H₂₆O₂S₂)], the Pd atom has a distorted square‐planar coordination geometry, with Pd—S distances of 2.3121 (18) and 2.3102 (18) Å, Pd—Cl distances of 2.291 (2) and 2.314 (2) Å, and S—Pd—Cl angles of 94.98 (7) and 86.25 (7)°. Upon complexation, an 11‐membered ring is formed by the S—Pd—S linkage in the ligand chain.